Method for detection of hydrocarbons



April 17, 1956 P. B. wElsz 2,742,574

METHOD FOR DETECTION OF HYDROCARBONS Filed Deo. l2, 1951 IN V EN TOR.

fhl /Vezlfz Y 2,742,574 l l., f METHOD Fon DETEcTloN oF HYDRocARBoNs Paul B. Weisz, Pitman, N. J., assignor` to Socony Mobil Oil Company, Inc., a corporation of New York Application December 12, 1951, Serial No. 261,348 l 1 claim. (ci. 25o-43.5)

yThis invention 'has to do with methods -for the detection offsmall amounts of hydrocarbons in gas samples containing the same.

In exploration for oil, one method which has receivedv attention is that of collecting soil-gas samples-from a series of points distributed in apattern across the area under examination, followed by analysis-of these soil-gas samples forhydrocarbons in an attempt todetermine whether or not the area examined has an underlying oil deposit. Y While many refinements o f technique have been worked outin the collection of samples, and their proper correlation with the possible underground deposits, one point of trouble has been the analysis4 of the samples. Classical methods of analysis have beenvapplied with difculty. Most methods of suitableaccuracy havebeen bench methods, adaptable for applicationonly,A in, a laboratory, usually at some distance from the pointof sample collection. Relatively few methods have been developed vshowing any promise vfor useat or near the` site of sample collection. The most desirable method'is one which can be expressed in apparatus combining high portability and accuracy, together with vruggedilessfin order that the soil-gas analysis couldbe` `conducted in the field, thus avoiding all of the inherent diiculties such as contamination, loss, and others arising from amethod which requires taking of samples in the field, transportation to a laboratory, and probably intervening storage prior to analysis. s

This invention is directed to a method for such analysis and for accomplishingssuch method.

It is further directed to a method for the analysiscapable of utilizing an apparatus of portable nature, adaptableto field use as well as laboratory use.

,The present method is based upon the 'fundamental proposition that in a Geiger-Muller counter, hydrocarbons of greater than" 2 carbon atoms are capable of actingas quenching media, as set forth in my prior United' States Patent 2,519,864. s. j l' g As is well known, a Geiger-Muller counter 'isa device for the detection of radiation, consisting essentially of a confined body of-gas, under low absolute pressurein which there are mounted two electrodes across which a high iield is maintained. When brought near a source of radiation, the arrival of an electron in this eld causes a discharge, which may be recorded as a count Suitable wiring arrangements for such equipment are well v known, as s also the fact that hydrocarbons of 2 or more carbon atoms, as well as other polyatomic gases, will act as quenchers in such G-M counters.

To more fully understand this invention, reference is now made to the drawings which are attached to and made a part of this specification.

In these drawings, Figure 1 shows, in highly diagrammatic form, the general arrangement `of the apparatus, while Figures 2 and 3 are representations of oscilloscope tracers obtained under described conditions of operation.

Referring now to Figure l, wherein is a Geiger- Muller counter tube, fed with gas of a desired nature ICC and a desired pressure through 11, which gas passesv out through 12, and equipped with electrodes 13 and 14. This counter should be operated in amanner customary for Seli-quenching operation. Assuming switches 15, 16, 17, 18 to be in positions opposite to those shown in the drawing, we havek a rather conventional Geiger-Muller counter setup, as follows: A potential is impressed across 13 and, 14 by battery 19 capable of variation by variable resistance 20. The value o f this voltage may be transferred, for recording purposes, to the horizontal sweep of Yan oscilloscope in conventionalv manner through switch 17, in the closed position. When an electron, originating in an adjacent source of radiation 22 enters chamber 10, the,A pulse resulting therefrom, passing through condenser 23 and a pulse rate counter circuit 24 of conventional nature, may be impressed upon the vertical sweep of oscilloscope 21 in conventional manner, switch 18 being closed directly to ground.

ner,.as for example by a continuous speed drive of known sort, the trace upon the face of oscilloscope 21 will be N,

the number of counts per interval of time (time being preselected within the counter circuit 24 in knownr manner), upon a vertical scale, against voltage upon a horizontal scale. The shape of the curve trace so drawn is f. dependent in great measure upon the nature of the gas mixture in chamber 10. v

- Turning to Figure 2, if a conventional mixture of say 8 parts argon and V1 part oxygen at a pressure of 5v to 10 centimeters of mercury (absolute) or ofS parts argon and.

1, part xylol, at similar pressure, or of any other mixture known .to the art as being an appropriate mixture ofargon and a quenching medium is fed to chamber 10, the trace willbe as shown at 25-26. For this trace, as indicated, voltage across theL G. M. tube is the horizontal scale,

increasing to the right, as indicated, and number of countsA per selected time interval is the vertical scale, increasing upwardly. The trace 25--26 shows a region 25..-27

v. where as voltage is increased, the counts increase proportionately, a plateau 27.-28 where thev number of counts remains relativelyhconst'ant across arrange of increasing voltage, and a range 28-26 wherer counts in.v crease again, passing toward continuous discharge, the upper limit of voltage V preferably being selected such that this condition will not be reached. Now, if, instead ofthe standard sort of mixture, a mixture of argon and soil-gas, containing a small amount of ethane be introduced to chamber 10, a trace such as 25-27--29-30 would be gotten (shown dotted for clarity). The plateau at 27--29 will result from the hydrocarbon, andy its nature, i.1e., its lengthhorizontally in terms of voltage,` and vertically in terms of N will depend upon the amount of hydrocarbon present. It may be quite small .upon a trace of normal size and consequently quite hard to detect. It may be rendered more capable of detection and lstudy-by effecting appropriate scale changesrin the oscilloscope, in the following manner:

Returning to Figure 1, this will be accomplished by operating resistance 20 manually and setting it at a voltage V1, corresponding to some point near or below the beginning 27, of the suspected plateau 27-29 (for V, 27,

29 see Figure 2). Then switches 15, 16, 17, 18 are brought to the positions shown. Now we have added to that voltage secured by setting of resistor 20, a voltage vderived from battery 31 and controlled by variable re- 3 ated over its range at constant speed, as by a motor drive. This voltage` being led. through `closed switch 16.to the horizontal sweep of oscillator 21. Amplifier 33, a voltage amplification circuit of anyconventional character,

in this voltage divider `to Ioscilloscope circuit, serves toJ multiply the horizontal or V scale for the oscilloscope trace. Amplier 33 may be fixed or variable. If itis so selected as to have `a gain ratio the same as the ratio between voltage sources 19-and 31, the expanded horizontal scalewill occupy the same actual horizontal distance upon the screen as did thebase scale. Obviously, if adjustable, greater orlessmagnitcation may be-had and this, together` with the preselected manual settingof voltage divider 20will'permit detailed examination of any portion ofthe oscilloscope trace.v As to the'vertical scale of the oscilloscopetrace, no'magnication is neces# sary, but it maybe desirable to be able Yto reset the position ofthe trace upon the'oscilloscope screen so that the point 27 (see Figure 2)-is `near the 'bottom of the screen. If this isvdesired, with switch18`-in the position shown in Figure 1, we have a voltage'source 34 and a -voltage divider 35, reverse in polarity to theimpulse `coming from pulse rate counting circuit124, which maybe used tov oppose (subtract) asuicient Vamount of that impulse `tolower the position of point 27g-upon the screen.

With these adjustments made, wehave a traceasshown in Figure 3, at 36-37 in which the plateau presenton the rst trace at 27-29 is magnified (ten times in the exemplary set up) in horizontalJ dimension, and rendered'far more detectable.

The course of operation to be followed is basically one of comparison of oscilloscope traces. A trace for albase condition will `be compared `withatrace-for a-soil gas sample. The comparison may-be.visual, or the-1 traces may be photographed, or any `of the usual, known, methods for handling data drawn from oscilloscope traces may be used. f f

The sensitivity of the arrangement is such'that hydro-Y carbons of C2 or greater will bedetectable if present in amounts as little as one partin Now to the method in more detail. The iirst step will be to operate with argon alone to get a basic-trace, which willhave no plateau. Then operate with `a mixture of argon and soil gas. If a plateau appears or is suspected, the scale shifting and scale `magnification arrangements are used, as desired, for itsistudy. In manycases, the basic trace maybe produced by'use-of argon mixed withr an appropriate known quencher.v In such case,'to minimize purging diic-ulties taking the basic trace -after examination of the samplesisadvisable. aftera given apparatus has been set up-and gotteninto` settled operation, the 'frequent taking of basic tracesmay prove unnecessary. v The relative concentration-of argon and sample gas in the tube atmosphere may be varied.y as desired-for sensitivity. Normally it Vwill be of.the=order offrom .1. to 50 parts (volume) ofsample with.99 to 50 parts ofargon. Otherwise, normal conditionsof `self-quenchingGM tube operation willA be practised, the. absolute pressure inthe tube-being dependent upon .the available voltage across In many cases, I"

d 4 the tube elements, as is well known It will be understood,. however, that I consider operating at pressures up. to and including atmospheric pressure as within the scope of my invention, such operation sometimes being advisable for the increase of sensitivity.

In the interpretation of results, it will be noted that when a plateau appears, it indicates the presence of a quencher, and that the length and slope of the plateau are indicative of its concentration. So, by use of suitable prepared samples for basic data, the method may be used to furnish not only knowledge of the presence of C2 and heavier hydrocarbons, but also to get a fair estimate of their concentration.

I claim:

A method of geophysical prospecting for investigating and evaluating the possibility of petroliferous deposits in underlying earth strata which includes the steps of collecting a soil gas sample from an underlying stratum to be investigated,'mixing the collected sample with aportion of a gaseous medium known to have non-quenchingchar- Vacteristics when placed in a Geiger counter, subjecting another portion Aof the gaseous medium mixedwith a gas havingknownfquenching characteristics to conditionssimulatingthat of'a Geiger counter, deriving an'output from the Geiger'counter indicative of the voltage and counts'relationshipfin the output of the Geiger counter, visuallydisplaying the voltage versus counts curve of'the output of the Geiger counter, said curve being characterd izedby a-definite plateau, recording thelvisual display and preserving ysame for subsequent use `as a reference,

subjecting themixture-of soil gas and gaseous medium. to'conditions simulatingthat of a Geiger counter, deriving an-outputV from ythe vGeiger counter indicative of thevoltage-and counts-relationship in the output of the Geiger counter; visuallyy i displaying the voltage versus counts cur've of the output of the Geigercounter,I detecting the presence of a plateau in the second mentioned curve by` reference/to therecord of the first-mentioned curve, magnifying'ffor visual inspection the second mentioned curve` in the vregion of any plateau, and deriving from the slope: and length` of any-magnified plateau of the second mentionedcurve` an indication of the presence of hydrocarbons ofat least two carbonatoms and their concentration.

References Cited in the file of this patent UNITED STATES PATENTS Heigl et al Mar. 9, 1948 Touvet July 10, 1951 OTHER REFERENCES 

